Composition and process for oxidative colouring keratin fibers

ABSTRACT

The present invention relates to a process for oxidative coloring keratin fibers especially human hair wherein dyeing composition comprises a cross linked copolymer. The objective of the present invention is a process for oxidative coloring hair wherein compositions A and B are mixed, composition A comprises at least one oxidative dye precursor and optionally at least one coupling agent and optionally at least one direct dye in a cosmetically acceptable medium and composition B comprises at least one oxidizing agent in a cosmetically acceptable medium, and applied onto hair and processed for 1 to 45 min at a temperature range of 20 to 45° C. and rinsed off from hair, wherein at least one of the two compositions A and B comprises a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid.

This application is a 371 application of PCT/EP2011/074012 filed Dec.23, 2011, which claims foreign priority benefit under 35 U.S.C. §119 ofEuropean Application No. 10016087.8 filed Dec. 27, 2010.

The present invention relates to a composition and a process foroxidative coloring keratin fibers especially human hair wherein dyeingcomposition comprises a cross linked copolymer.

Oxidative coloring is carried out by applying onto hair a mixture of twocompositions which are kept separate till short before application andafter certain processing time the hair is rinsed off. For a successfulcolor result, it is very important that the applied dyeing agent staysat the site of application during the entire period of processing.Currently, emulsions with certain consistency and also thickenedcompositions are used in practice. The drawbacks are practicing withhighly sensible compositions such as instability of emulsions in thepresence of high salt concentrations on one hand, and on the other hand,inacceptable hair properties in terms of combability, flyaways,elasticity when conventional thickeners are used. Due to inacceptablehair conditioning and feel, consumers often have to use additionalproducts in order to restore and/or bring hair feel to a acceptablelevel. This is on one hand time consuming and on the other hand bringsunnecessary additional costs.

The aim of the present invention is to provide a hair dyeing processwith compositions having appropriate consistency after mixing and alsoleave hair in a cosmetically acceptable form so that use of additionalhair cosmetic compositions is largely avoided.

The objective of the present invention is a process for oxidativecoloring hair wherein compositions A and B are mixed, composition Acomprises at least one oxidative dye precursor and optionally at leastone coupling agent and optionally at least one direct dye in acosmetically acceptable medium and composition B comprises at least oneoxidizing agent in a cosmetically acceptable medium, and applied ontohair and processed for 1 to 45 min at a temperature range of 20 to 45°C. and rinsed off from hair, wherein at least one of the twocompositions A and B comprises a cross linked copolymer ofvinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium andmethacrylic acid.

Further objective of the present invention is the use of the inventiveprocess for homogeneous colouring and conditioning of keratin fibers,especially human hair.

In a preferred embodiment of the present invention, both compositions Aand B comprise a cross linked copolymer of vinylpyrrolidone,vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid.

Suitable and the most preferred polymer is Polyquaternium-86 which iscommercially available under the trade name Luvigel Advanced from BASF.

Still further object of the present invention is a compositioncomprising at least one hair dye and a cross linked copolymer ofvinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium andmethacrylic acid, wherein at least one hair dye is preferably selectedfrom oxidative hair dye precursors and direct dyes which may be anionic,cationic and neutral dye. Further preferred embodiment of the presentinvention is that the composition comprises at least one oxidizingagent, preferably hydrogen peroxide.

Concentration of the polymer is in the range of 0.01 to 10%, preferably0.05 to 7.5, more preferably 0.1 to 5% and most preferably 0.2 to 5% byweight calculated to total of each composition.

Composition A, or a composition for dyeing as described above, comprisesat least one oxidative dye precursor. Non-limiting examples todevelopers are p-phenylenediamines and substituted p-phenylenediaminessuch as 2,5-diamino-toluene, 2-n-propyl or 2-ethyl-p-phenylenediamine,2,6-di-methyl-p-phenylenediamine, 2-(2,5-diaminophenyl)ethanol,1-amino-4-bis-(2′-hydroxyethyl)amino-benzene, 2-(2-hydroxyethylamino)-5-aminotoluene, 4,4′-diaminodiphenylamine, 4-aminodiphenylamine,2-amino-5-N,N-diethyl aminotoluene, 4-amino-N-ethyl-N-isopropyl aniline,2-chloro-p-phenylenediamine,1-β-hydroxyethyl-2,5-diamino-4-chlorobenzene,1-β-hydroxyethyl-2,5-diamino-4-methyl benzene,2-methoxy-p-phenylenediamine, N,N-diethyl-p-phenylenediamine,1-amino-4-β-methoxyethyl aminobenzene, 1-dimethyl-amino-4-aminobenzene,1-hydroxy-2,5-diamino-4-methyl benzene,1-hydroxymethyl-2,5-diaminobenzene, 1,3-dimethyl-2,5-diaminobenzene,1,4-diamino isopropyl benzene and/or 1-amino-4-β-hydroxypropylaminobenzene, pyrazole and the derivatives thereof such as1-hydroxyethyl-4,5-diaminopyrazole, 3,4-diamino-5-hydroxypyrazole,3,5-diaminopyrazole, 3,5-diamino pyrazol-1-carboxamide,3-amino-5-hydroxypyrazole, 1-phenyl-2-methylpyrazole,1-phenyl-3-methylpyrazole-5-one, 3,5-dimethylpyrazole,3,5-dimethylpyrazole-1-methanol, 3,5-diamino-1,2,4-triazole,2-aminophenol, 4-aminophenol and the derivatives thereof such as4-amino-3-methylphenol, 2-chloro-4-aminophenol,2,6-dichloro-4-aminophenol, 2,4-diamino-phenol,2,6-dibromo-4-aminophenol, 5-amino salicylic acid and/or 1,2,4-triaminobenzene or the water-soluble salts thereof.

Suitable tetraminopyrimidines are in particular2,4,5,6-tetraminopyrimidine and the lower alkyl derivatives thereof;suitable triaminohydroxypyrimidines are, for example4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidineand 5-hydroxy-2,4,6-triaminopyrimidine; suitable mono- and diaminodihydroxypyrimidines are, for example,2,6-dihydroxy-4,5-diaminopyrimidine, 2,4-diamino-6-hydroxy-pyrimidine or4,6-dihydroxy-2,5-diaminopyrimidine or the water-soluble salts thereof;a preferred amino-substituted triazine is 2,4-diamino-1,3,5-triazine.

Composition A or a composition for dyeing as described above,furthermore optionally comprises at least one coupling agent. Suitablenon-limiting examples are resorcinol, 2-methyl resorcinol,4-chlororesorcinol, 2-amino-4-chlorophenol,5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3-amino-phenol,1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethyl aminophenol,2,6-dihydroxy-3,5-dimethoxypyridine, 5-amino-3-methylphenol,6-amino-3-methylphenol, 3-amino-2-methylamino-6-methoxypyridine,2-amino-3-hydroxy-pyridine, 2-dimethyl-amino-5-aminopyridine,2,6-diaminopyridine, 1,3-diamino-benzene,1-amino-3-(2′-hydroxyethylamino)benzene,1-amino-3-[bis(2′-hydroxy-ethyl)amino]benzene, α-naphthol,4,6-dichlororesorcinol, 1,3-diamino-toluene, 1-hydroxy naphthalene,4-hydroxy-1,2-methylenedioxy benzene, 1,5-dihydroxy naphthalene,1,6-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 2,7-dihydroxynaphthalene, 1-hydroxy-2-methyl naphthalene, 4-hydroxy-1,2-methyldioxybenzene, 2,4-diamino-3-chlorophenol, 5-amino-2-methoxyphenol and/or1-methoxy-2-amino-4-(2′-hydroxyethyl amino)benzene or the water-solublesalts thereof.

However, this shall not exclude the addition of further developing andcoupling substances.

The total concentration of the developing substances customarily rangesbetween about 0.05% and 5%, preferably 0.1% and 4%, in particular 0.25%to 3% by weight, calculated to the total hair dyeing compositionexcluding the oxidation agent.

In the hair dyeing compositions, the coupling substance(s) as reactionpartners of the developing substance(s) are present in approximately thesame molecular proportions as the developing substances, i.e. in amountsfrom 0.01% to 5.0%, preferably 0.05% to 4%, in particular 0.1% to 3% byweight, calculated to the total composition excluding the oxidizingagent.

The preferred weight proportion of the named developing substances tothe coupling substances ranges between about 1:8 to 8:1, preferablyabout 1:5 to 5:1, in particular 1:2 to 2:1.

Oxidative colouring compositions, Composition A, a composition fordyeing as described above, comprises direct dyes of neutral, cationicand anionic ones.

Non-limiting examples to neutral HC dyes are HC Blue No. 2, HC Blue No.4, HC Blue No. 5, HC Blue No. 6, HC Blue No. 7, HC Blue No. 8, HC BlueNo. 9, HC Blue No. 10, HC Blue No. 11, HC Blue No. 12, HC Blue No. 13,HC Brown No. 1, HC Brown No. 2, HC Green No. 1, HC Orange No. 1, HCOrange No. 2, HC Orange No. 3, HC Orange No. 5, HC Red BN, HC Red No. 1,HC Red No. 3, HC Red No. 7, HC Red No. 8, HC Red No. 9, HC Red No. 10,HC Red No. 11, HC Red No. 13, HC Red No. 54, HC Red No. 14, HC VioletBS, HC Violet No. 1, HC Violet No. 2, HC Yellow No. 2, HC Yellow No. 4,HC Yellow No. 5, HC Yellow No. 6, HC Yellow No. 7, HC Yellow No. 8, HC

Yellow No. 9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HCYellow No. 13, HC Yellow No. 14, HC Yellow No. 15,2-Amino-6-chloro-4-nitrophenol, picramic Acid,1,2-Diamino-4-nitrobenzol, 1,4-Diamino-2-nitrobenzol,3-Nitro-4-aminophenol, 1-Hydroxy-2-amino-3-nitrobenzol,2-Hydroxyethylpicramic acid, 2-amino-4.6-dinitrophenol,2-amino-4-nitrophenol, and 2-amino-6-chloro-4-nitrophenol.

Cationic direct dyes as disclosed in the patent applications EP 1166752,EP 1172082 and EP 970684 and as well WO 95/01772 are suitable for thecomposition A of the present invention. Non-limiting examples are BasicBlue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, BasicBlue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7,Basic Green 1, Basic Red 2, Basic Red 12 Basic Red 22, Basic Red 51,Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, BasicViolet 10, Basic Violet 14, Basic Yellow 87, Basic Yellow 57, and BasicOrange 31. Preferred cationic dyes are especially Basic Yellow 87, BasicOrange 31 and Basic Red 51.

Suitable non-limiting examples to anionic dyes are Acid Black 1, AcidBlue 1, Acid Blue 3, Food Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue74, Acid Orange 3, Acid Orange 6, Acid Orange 7, Acid Orange 10, AcidRed 1, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 50, Acid Red 52,Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 155, AcidRed 180, Acid Violet 9, Acid Violet 43, Acid Violet 49, Acid Yellow 1,Acid Yellow 23, Acid Yellow 3, Food Yellow No. 8, D&C Brown No. 1, D&CGreen No. 5, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 10, D&COrange No. 11, D&C Red No. 21, D&C Red No. 27, D&C Red No. 33, D&CViolet 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, FD&CRed 2, FD&C Red 40, FD&C Red No. 4, FD&C Yellow No. 6, FD&C Blue 1, FoodBlack 1, Food Black 2, Disperse Black 9 and Disperse Violet 1 and theiralkali metal salts such as sodium, potassium. Among those, the preferredanionic dyestuffs are Acid Red 52, Acid Violet 2, Acid Red 33, AcidOrange 4, Acid Red 27 and Acid Yellow 10 and their salts. The mostpreferred anionic dyes are Acid Red 52, Acid Violet 2, Acid Red 33, AcidOrange 4 and Acid Yellow 10, and their salts

Concentration of one or more direct dyes in total is in the range of0.001 to 5% by weight, preferably 0.01 to 4% more preferably 0.05 to 3%and most preferably 0.1 to 2.5% by weight calculated to totalcomposition.

Composition A, a composition for dyeing as described above, comprisesadditionally at least one alkalizing agents. Suitable ones are ammoniaand alkyl or alkanol amines such as monoethanol amine, triethanol amineetc. Concentration of alkalizing agent is dependent on the alkalinityvalue aimed is in the range of 0.1 to 20%, preferably 0.2 to 15% andmore preferably 0.5 to 10% by weight calculated to total compositionexcluding oxidizing agent.

Composition B, a composition for dyeing as described above, comprises atleast one oxidizing agent. The preferred oxidizing agent is hydrogenperoxide, for example in a concentration of 2 to 12% by weight. However,the use of other peroxides such as urea peroxide and melamine peroxideis also possible.

The pH-value of the ready-to-use hair dyeing composition, i.e. aftermixing with peroxide, is in the range of 2 to 11, preferably 5 to 10.5,more preferably 6 to 10 and most preferably 6.5 to 9.5.

Ready to use composition of the present invention has a viscosity in therange of 1000 to 25000 mPa·s measured at 20° C. with Brookfieldviscometer using an appropriate spindle. Preferably the viscosity of theready to use composition is in the range of 2500 to 20000 mPa·s and morepreferably 5000 to 20000 mPa·s. and most preferably 7500 to 15000 mPa·s.measured at 20° C.

In a further preferred embodiment of the present invention, apretreatment composition is applied onto hair prior to application ofoxidative dyeing composition. Pretreatment composition comprises atleast one compound such as inorganic salt and/or dihydroxyacetone whichcatalyzes and/or affects the oxidative colour development reaction fromoxidative dyes precursors, and optionally rinsed off from hair. Suitablenon-limiting inorganic salts are salts of iodide ions especiallypotassium and sodium salts, copper chloride, copper sulphate, cobaltchloride, cerium sulphate, cerium chloride, vanadium sulphate, lithiumchloride, potassium dichromate, magnesium acetate, calcium chloride,calcium nitrate, barium nitrate, magnesium oxide, ammonium nitrate andammonium chloride. Preferred are salts of iodide ions especiallypotassium and sodium salts, copper chloride, copper sulphate, cobaltchloride, cerium sulphate, cerium chloride, vanadium sulphate, lithiumchloride, potassium dichromate, magnesium acetate, calcium chloride,calcium nitrate, barium nitrate and magnesium oxide. Most preferred arethe salts of iodide ions and especially sodium and potassium salts andin particular potassium iodide. It is furthermore appropriate to usesuitably any combination of inorganic salts, two or more salts,catalyzing and/or effecting the oxidative colour development reactionfrom oxidative dyes precursors.

Concentration of at least one inorganic salt and/or dihydroxyacetone inthe aqueous composition is typically from 0.01 to 20%, preferably 0.05to 15% and most preferably 0.1 to 10% and in particular 0.2 to 7.5% byweight calculated to the total composition. The concentration rangesdisclosed herein are the total concentration of the inorganic salts incase more then one is used in mixture.

In a preferred embodiment, aqueous composition comprising at least oneinorganic salt is processed up to 20 min, preferably up to 15 min andmore preferably up to 10 min with or without using heat, preferably at atemperature range between 20 and 45° C., on hair prior to application ofoxidative dyeing composition.

In a preferred embodiment of the present invention, pretreatmentcomposition comprises as well a cross linked copolymer ofvinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium andmethacrylic acid, preferably Polyquaternium-86 at the above mentionedconcentration ranges.

Viscosity of the pretreatment composition is also in the range of 1000to 25000 mPa·s measured at 20° C. with Brookfield viscosmeter using anappropriate spindle. Preferably the viscosity of the pretreatmentcomposition is in the range of 2500 to 20000 mPa·s and more preferably5000 to 20000 mPa·s. and most preferably 7500 to 15000 mPa·s. measuredat 20° C.

pH of the pretreatment composition is preferably in the range of 5 to10.

Any of the aqueous compositions used in the inventive process of thepresent invention as disclosed above can comprise one or more of thefollowing ingredients.

One or more of aqueous compositions may comprise additional thickeningpolymer of any kind, namely, anionic, cationic, nonionic and/oramphoteric polymers. Natural polymers such as chitosan and itsderivatives, cellulose and its derivatives and hydroxyethylcellulose andguar gum and their derivatives may be comprised in any of the aqueouscompositions used in the novel process of the present invention. Itshould be noted that the concentration of the additional thickeningpolymer should be lower than the concentration of the cross linkedcopolymer of vinylpyrrolidone, vinylimidazol,3-methyl-1-vinylimidazolium and methacrylic acid, preferablyPolyquaternium-86.

One or more of aqueous compositions may comprise cationic polymers asconditioning agents which enhances first of all combability andtherefore makes applications onto hair easier which may alsoadditionally have thickening effect. Those are cationic cellulose typepolymers know as Polymer JR type from Amerchol such as Polyquaternium 10or cationic guar gum known with trade name Jaguar from Rhône-Poulenc andchemically for example Guar hydroxypropyl trimonium chloride.Furthermore. chitosan and chitin can also be included in thecompositions as cationic natural polymers.

Furthermore, those cationic polymers known with their CTFA category namePolyquaternium may as well be added into pre-treatment compositions ofthe present invention. Typical examples of those are Polyquaternium 6,Polyquaternium 7, Polyquaternium 10, Polyquaternium 11, Polyquaternium16, Polyquaternium 22 and Polyquaternium 28, Polyquaternium 30,Polyquaternium 37, Polyquaternium 36, Polyquaternium 46, Polyquaternium87, Polyquaternium 67.

The cationic polymers also include the quaternized products of graftpolymers from organopolysiloxanes and polyethyl oxazolines described inEP-A 524 612 and EP-A 640 643.

Concentration of the polymers of anionic, cationic, non-ionic and/oramphoteric or zwitterionic character mentioned above is in the range of0.05-10%, preferably 0.1-7.5%, preferably 0.2-7.5% and most preferably0.2-5% by weight, calculated to the total composition.

One or more of aqueous compositions of inorganic salt may comprise oneor more surfactants selected from non-ionic, anionic, cationic andamphoteric ones. The surfactants suitable for the compositions arenonionic surfactants. Preferred nonionic surfactants are ethoxylatedfatty alcohols according to the following formula:R₁(CH₂CH₂O)_(n)Hwhere R₁ is a saturated or unsaturated, linear or branched alkyl chainwith 12 to 22 C atoms and n is a number between 2 and 50 preferably 2 to40, more preferably 2 to 30. In one of the preferred embodiments of theinvention, the hair treatment compositions comprise a mixture of twononionic fatty alcohol ethoxylates, one has between 2 to 10 ethoxylateunits and the other is more than 10. Those surfactants are known by thegeneric terms for example “Laureth”, “Myristeth”, “Oleth”, “Ceteth”,“Deceth”, “Steareth” and “Ceteareth” according to the CTFA nomenclature,including addition of the number of ethylene oxide molecules. e.g.Ceteareth-20, Steareth-2.

Further nonionic surfactants suitable are those polyethylene glycolethers of monoglycerides according to the general formula

R₁ and n are same as above. Examples to those types of nonionicsurfactants are PEG-7-glyceryl cocoate known with the trade name CetiolHE from Cognis, PEG-8-glyceryl laurate know with the trade name GlyceroxL8 from Croda Chemicals, PEG-10 glyceryl oleate, PEG-15 glycerrylisostearate, PEG-5 glycerryl stearate, PEG-15 glyceryl ricinoleate, etc.

Further nonionic surfactants suitable are alkyl polyglucosides of thegeneral formulaR₂—O—(R₃O)_(n)—Z_(x).wherein R₂ is an alkyl group with 8 to 18 carbon atoms, R₃ is anethylene or propylene group, Z is a saccharide group with 5 to 6 carbonatoms, n is a number from 0 to 10 and x is a number between 1 and 5.

Additionally useful nonionic surfactants are the various sorbitanesters, such as polyethylene glycol sorbitan stearic acid ester, fattyacid polyglycol esters or poly-condensates of ethyleneoxide andpropyleneoxide, as they are on the market, for example, under the tradename “Pluronics®”, as well as fatty alcohol ethoxylates.

Still further suitable nonionic surfactants are amineoxides. Suchamineoxides are known especially because of their use in cleansingcompositions, for example C₁₂-C₁₈-alkyl dimethyl amineoxides such aslauryl dimethyl amineoxide, C₁₂-C₁₈-alkyl amidopropyl or -ethylamineoxides, C₁₂-C₁₈-alkyl di(hydroxyethyl) or (hydroxypropyl)amineoxides, or also amineoxides with ethyleneoxide and/orpropyleneoxide groups in the alkyl chain, Those are on the market, forexample, under the trade names “Ammonyx®”, “Aromox®” or “Genaminox®”.

Anionic surfactants of the sulfate, sulfonate, carboxylate types are aswell suitable in compositions of the present invention. Those are theones very commonly used in cosmetic cleansing preparations, for example,the known C₁₀-C₁₈-alkyl sulfates, and in particular the respective ethersulfates, for example, C₁₂-C₁₄-alkyl ether sulfate, lauryl ethersulfate, especially with 1 to 4 ethylene oxide groups in the molecule,monoglyceride (ether) sulfates, fatty acid amide sulfates obtained byethoxylation and subsequent sulfatation of fatty acid alkanolamides, andthe alkali salts thereof.

Additional anionic surfactants are α-olefin sulfonates or the saltsthereof, and in particular alkali salts of sulfosuccinic acidsemiesters, for example, the disodium salt of monooctyl sulfosuccinateand alkali salts of long-chain monoalkyl ethoxysulfosuccinates.

Suitable surfactants of the carboxylate type are alkyl polyethercarboxylic acids and the salts thereof of the formulaR₆—(C₂H₄O)_(n)—O—CH₂COOX.wherein R₆ is a C₈-C₂₀-alkyl group, preferably a C₁₂-C₁₄-alkyl group, nis a number from 1 to 20, preferably 2 to 17, and X is H or preferably acation of the group sodium, potassium, magnesium and ammonium, which canoptionally be hydroxyalkyl-substituted, as well as alkyl amido polyethercarboxylic acids of the general formula

wherein R₆ and X have the above meanings, and n is in particular anumber from 1 to 10, preferably 2.5 to 5.

Such products have been known for some time and are on the market, forexample, under the trade name “AKYPO®” and “AKYPO-SOFT®”.

Also useful are C₈-C₂₀-acyl isethionates, alone or in mixture with otheranionic surfactants, as well as sulfofatty acids and the esters thereof.

It is also possible to use mixtures of several anionic surfactants inmixture within the scope of the invention.

Further suitable anionic surfactants are also C₈-C₂₂-acylaminocarboxylic acids or the water-soluble salts thereof. Especiallypreferred is N-lauroyl glutamate, in particular as sodium salt, as wellas, for example, N-lauroyl sarcosinate, N—C₁₂-C₁₈-acyl asparaginic acid,N-myristoyl sarcosinate, N-oleoyl sarcosinate, N-lauroyl methylalanine,N-lauroyl lysine and N-lauroyl aminopropyl glycine, preferably in formof the water-soluble alkali or ammonium, in particular the sodium saltsthereof, preferably in admixture with the above-named anionicsurfactants.

As further surfactant component, one or more of aqueous compositions maycomprise amphoteric or zwitterionic surfactants.

Useful as such are in particular the various known betaines such asalkyl betaines, fatty acid amidoalkyl betaines and sulfobetaines, forexample, lauryl hydroxysulfobetaine; long-chain alkyl amino acids, suchas cocoaminoacetate, cocoaminopropionate and sodium cocoamphopropionateand -acetate have also proven suitable.

Cationic surfactants may also be comprise in one or more aqueouscompositions and particularly as conditioning agent and according to thegeneral formula

where R₈ is a saturated or unsaturated, branched or non-branched alkylchain with 8-22 C atoms orR₁₂CONH(CH₂)_(n)where R₁₂ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4 orR₁₃COO(CH₂)_(n)where R₁₃ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4. andR₉ is a lower alkyl chain with 1 to 4 carbon atoms, saturated orunsaturated, branched or non-branched alkyl chain with 8-22 C atoms orR₁₂CONH(CH₂)_(n)where R₁₂ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4 orR₁₃COO(CH₂)_(n)where R₁₃ is saturated or unsaturated, branched or non-branched alkylchain with 7-21 C atoms and n has typical value of 0-4. andR₁₀ and R₁₁ are independent from each other lower alkyl chain with 1 to4 carbon atoms, and X is chloride, bromide or methosulfate.

Suitable cationic surfactants and or conditioning agents are, forexample, long-chain quaternary ammonium compounds which can be usedalone or in admixture with one another, such as cetyl trimethyl ammoniumchloride, myristoyl trimethyl ammonium chloride, trimethyl cetylammonium bromide, stearyl trimethyl ammonium chloride, dimethyl stearylammonium chloride, dimethyl dihydrogenated tallow ammonium chloride,stear trimonium chloride, dipalmitoyl dimonium chloride, distearyldimethyl ammonium chloride, stearamidopropyl trimonuim chloride anddioleoylethyl dimethyl ammonium methosulfate, etc.

From the above quaternary ammonium compounds disclosed with the generalformula, especially preferred as hair conditioning agents are thosecompounds known per se and are on the market, for example, under thetrade names “Schercoquat®”, “Dehyquart® F30” and “Tetranyl®”.

Again from the above quaternary ammonium compounds disclosed with thegeneral formula, especially preferred as conditioning ingredient arethese compounds are known per se and on the market, for example, underthe trade name “INCROQUAT® HO” or “OCS”. Those compounds are known witha general ingredient category under “amidoquat” in the cosmeticindustry.

According to present invention total concentration of surfactants ofanionic, cationic, non-ionic and/or amphoteric or zwitterionic characteris in the range of 0.05-10%, preferably 0.05-7.5% and most preferably0.05-5% by weight, calculated to the total composition of eachcomposition.

One or more of aqueous composition can also comprise conditioning agentsselected from oily substances and nonionic substances. Oily substancesare selected from such as silicone oils volatile or non-volatile,natural and synthetic oils. Among silicone oils those can be addedinclude dimethicone, dimethiconol, polydimethylsiloxane, DC fluid rangesfrom Dow Corning, arylated silicones, aminated silicones, natural oilssuch as olive oil, almond oil, avocado oil, wheatgerm oil, ricinus oiland the synthetic oils, such as mineral oil.

Non-ionic conditioning agents may be polyols such as glycerin, glycoland derivatives, polyethyleneglycoles known with trade names CarbowaxPEG from Union Carbide and Polyox WSR range from Amerchol, polyglycerin,polyethyleneglycol mono or di fatty acid esters.

Conditioners mentioned above can be contained at a concentration ofbelow 1%, preferably below 0.75% by weight, calculated to totalcomposition.

One or more of the aqueous compositions can comprise one or more organicsolvent. Examples are such as ethanol. propanol, isopropanol, benzylalcohol, benzyloxyethanol, alkylene carbonates such as ethylenecarbonate and propylene carbonate, phenoxyethanol, butanol, isobutanol,cyclohexane, cyclohexanol, hexyleneglycol, ethylenecarbonate,ethyleneglycol monoethylether, ethylene glycol monobutyl ether, ethyleneglycol monophenyl ether, 1-phenylethylalcohol, 2-phenylethylalcohol,o-methoxyphenol. Concentration of one or more organic solvents is in therange of 1 to 25%, preferably 1 to 20%, more preferably 1 to 15% andmost preferably 1 to 10% by weight, calculated to the total composition.

One or more of the compositions may comprise at least one ubiquinone ofthe formula

where n is a number between 1 and 10 at a concentration of 0.0001 to 1%,preferably from 0.0002 to 0.75%, more preferably from 0.0002 to 0.5% andmost preferably from 0.0005 to 0.5% by weight, calculated to total ofeach composition.

The compositions comprise ubiquinone which is preferably selected fromthe ones where n is a number between 6 and 10 and more preferably it isubichinone 50 where n is 10, also known as Coenzyme Q10.

One or more of the aqueous composition can comprise at least one aminoacid. At least one amino acid is comprised at a concentration of 0.01 to10%, preferably 0.05 to 7.5% and more preferably 0.1 to 5% and mostpreferably 0.25 to 5% by weight calculated to total of each composition.

Suitable amino acids are glycin, histidine, citrullin, asparagine,alanin, valin, leucin, isoleucin, pyrrolin, tryptophane, phenylalanine,methionine, serine, tyrosine, threonine and gluatamine. Preferably, theamino acid is selected from glycin, histidine, citrullin, asparagine,alanin, valin, leucin, isoleucin, pyrrolin, serine, tyrosine, threonineand gluatamine. More preferably, at least one amino acid is selectedfrom glycin, histidine, asparagine, alanin, valin, leucin, pyrrolin,serine, tyrosine and gluatamine, and most preferably at least one aminoacid is selected from glycin, asparagine, alanin, valin, leucin, andserine.

One or more of the aqueous composition can comprise further ceramidetype of compound with the general formula

where R₂₀ and R₂₁ are independent from each other alkyl- or alkenylgroup with 10 to 22 carbon atoms, R₂₂ is alkyl or hydroxyl alkyl with 1to 4 carbon atoms group and n is a number between 1 to 6, preferably 2or 3. Preferred compound according to the above chemical structure iscetyl-PG-hydroxyethylpalmitamide.

Further optional ingredient are sterols, especially the phytosterols aspreferred hair restructuring agents. Especially preferred ones are ofplant origin for example ergosterol, sitosterol, stigmasterol,fucosterol, brassicasterol, fungisterol, campesterol, zymosterol,ascosterol, cerevisterol, episterol, faecosterol, spinasterol. Amongthose phytosterols, the ones found in “Avocadin” which is theunsaponified fraction of the avocado oil is more preferred.

Optionally fatty acids of C₁₀ to C₂₂ may be incorporated into thecompositions of the present invention at a concentration of preferably0.01 to 2.5% by weight calculated to total of each composition.

In a further preferred embodiment of the present invention, One or moreof the aqueous composition can comprise at least one diamine compound.Preferred diamide compounds are according to the general structure

wherein R₂₅ is a linear or branched, saturated or unsaturated alkylchain with 1 to 12 C atoms which may be substituted with hydroxy and/oralkoxy groups, preferably R₂₅ is linear or branched, saturated orunsaturated alkyl chain with 1 to 12 C atoms which may be substituted by1 to 3 substituents selected from a hydroxy group and C1 to C6 alkoxygroup, more preferably R₂₅ is a unsubstituted alkyl group with 1 to 12 Catoms, and alkyl group with 2 to 12 C atoms substituted by one or twohydroxyl groups, by one alkoxy group with 1 to 6 C atoms or by onehydroxyl and one alkoxy group with 2 to 6 C atoms, R₂₆ is linear orbranched alkyl chain with 1 to 5 C atoms, preferably linear or branchedalkyl chain with 2 to 5 C atoms and more preferably an alkyl chain with2 to 3 C atoms, and R₂₇ linear or branched, saturated or unsaturatedalkyl chain with 1 to 22 C atoms, preferably linear or branched,saturated or unsaturated alkyl chain with 11 to 22 C atoms.

Preferred individual diamide compounds are the ones according to theformula A to G.

Particularly preferred diamide compound is the compound F which is bis(methoxypropylamido) isodocosane and commercially available from KaoCorporation-Japan.

Concentration of diamide compounds in the intermediate treatmentcompositions of the present invention is in the range of 0.001 to 5%,preferably 0.002 to 3% more preferably 0.005 to 2% and most preferably0.01 to 1% by weight calculated to total of each composition.

Another preferred compound, one or more of the aqueous compositionscomprise silicone compounds and especially aminated silicones such asamodimethicone available from for example Dow Corning under the brandnames Dow Corning 949 Emulsion and Dow Corning 2-8194 ME. Concentrationof silicones, especially amodimethicone, is in the range of 0.05 to2.5%, preferably 0.1 to 1% by weight calculated to total or eachcomposition.

Additionally, one or more natural oil may be incorporated into the oneor more of the aqueous compositions of the present invention. Suitableare such as olive oil, almond oil, avocado oil, wheatgerm oil, ricinusoil or their mixture. Concentration of these natural oil ingredientsshould be 0.01 to 2.5%, preferably 0.01.to 1%, more preferably 0.05 to0.5% by weight, calculated to total each composition.

The compositions used in the inventive process of the present inventionare preferably provided in a kit. Accordingly further objective of thepresent invention is a kit for oxidative dyeing keratin fiberspreferably hair comprising

-   -   a—optionally an aqueous composition comprising at least one        organic salt and/or dihydroxyacetone,    -   b—a composition comprising at least one hair dye wherein at        least one hair dye is preferably selected from oxidative hair        dye precursors and direct dyes which may be anionic, cationic        and neutral dye,    -   c—an aqueous composition comprising at least one oxidizing        agent,        with the condition that at least one of the above compositions,        preferably composition b, more preferably compositions b and c        comprise a cross linked copolymer of vinylpyrrolidone,        vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid,        preferably Polyquaternium-86.

The following examples are to illustrate the invention, but not to limitit.

EXAMPLE 1

% by weight Stearyl alcohol 8.0 Coco fatty acid monoethanolamide 4.51,2-Propanediol mono/distearate 1.0 Coco fatty alcohol polyglycol ether4.0 Sodium lauryl sulphate 1.0 Oleic acid 2.0 Propanediol 2.0 Sodiumsulfite 1.0 Luvigel Advanced 1.0 Ascorbic acid 0.5 EDTA 0.5 Ammonia 1.0p-toluenediamine sulhate 0.74 4-chlorresorcinol 0.24 Resorcinol 0.08m-aminophenol 0.06 4-amino-2-hydroxytoluene 0.02 Water to 100

The tests were carried out with swatches of bleached human hair. Thecoloring compositions were obtained after mixing the above givencomposition comprising dyestuff precursors with oxidizing agentcomprising 4% by weight hydrogen peroxide at a mixing ratio of 1:1 byweight. The pH of the resulting mixture was 9.8.

Hair coloured with the above composition for 30 min at ambienttemperature was homogeneously coloured. It was observed that hair waseasily combable, soft, with natural bounce and elasticity and had lessflyaways. Exclusion of Luvigel Advanced resulted in loss of effects.

EXAMPLE 2

The compositions of Example 1 were used wherein oxidizing compositioncomprising 4% by weight hydrogen peroxide comprised additionally 0.5% byweight Luvigel Advanced. Hair was coloured homogeneously and wascombable, softer and had less flyaways. It was observed that shine wasalso significantly improved. Exclusion of Luvigel Advanced resulted inloss of effects.

EXAMPLE 3

The compositions of Example 1 were used

Additionally hair was treated first with a pretreatment composition ofthe following composition

% by weight Potassium iodide 2.5 Luvigel Advanced 0.5 Monoethanolamine4.8 Hydrochloric acid 4.0 Water q.s. to 100 pH of the above compositionwas 8.0.

Hair was treated first with pretreatment composition of the abovecomposition for 10 min and without rinsing off oxidative dyeingcomposition as in Example 1 was applied and after 30 min. rinsed offfrom hair and hair was dried. Hair was coloured homogeneously and wascombable, soft and had less flyaways and had natural elasticity. It wasobserved that shine was also significantly improved. Exclusion ofLuvigel Advanced resulted in loss of effects.

The invention claimed is:
 1. A process for oxidative dyeing keratin fibers comprising: mixing compositions A and B to form a mixture, wherein composition A comprises at least one oxidative dye precursor and, optionally, at least one coupling agent and, optionally, at least one direct dye in a cosmetically acceptable medium, and further wherein composition B comprises at least one oxidizing agent in a cosmetically acceptable medium; and applying the mixture onto the keratin fibers and processing for 1 to 45 min at a temperature range of 20 to 45° C. and rinsing the mixture off from the keratin fibers, wherein at least one of the two compositions A and B comprises a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid.
 2. The process according to claim 1, wherein both compositions A and B comprise a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid.
 3. The process according to claim 1, wherein the cross linked copolymer is Polyquaternium-86.
 4. The process according to claim 1, wherein the cross linked copolymer is present at a concentration range of 0.01 to 10% by weight calculated to total of each composition.
 5. The process according to claim 1, wherein composition A further comprises at least one alkalizing agent.
 6. The process according to claim 1, wherein the mixture obtained after mixing of compositions A and B has a pH between 2 to
 11. 7. The process according to claim 1, wherein composition B further comprises hydrogen peroxide as an oxidizing agent.
 8. The process according to claim 1, wherein the mixture obtained after mixing of compositions A and B has a viscosity in the range of 1000 to 25000 mPa·s measured at 20° C. with Brookfield viscosi.
 9. A process according to claim 1 further comprising: applying onto the kerating fibres pretreatment composition comprising at least one compound, catalyzing or effecting the oxidative colour development reaction from oxidative dye precursors, processing up to 20 min, and optionally, rinsing off the pretreatment composition from keratin fibres prior to application of the mixture of compositions A and B.
 10. The process according to claim 9, wherein the pretreatment composition comprises at least one inorganic salt and/or dihydroxyacetone as compound catalyzing and/or effecting the oxidative colour development reaction from oxidative dye precursors.
 11. The process according to claim 9, wherein the pretreatment composition comprises a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid.
 12. The process according to claim 1, wherein one or more of the compositions A and B comprise one or more of the compounds selected from surfactants, conditioning agents, ubiqinones of the formula

where n is a number between 1 and 10, amino acid, ceramide type of compound according to general formula

where R₂₀ and R₂₁ are independent from each other alkyl- or alkenyl group with 10 to 22 carbon atoms, R₂₂ is alkyl or hydroxyl alkyl with 1 to 4 carbon atoms group and n is a number between 1 to 6, sterol, especially phytosterol, diamide compounds according to general structure

wherein R₂₅ is a linear or branched, saturated or unsaturated alkyl chain with 1 to 12 C atoms which may be substituted with hydroxy and/or alkoxy groups, preferably R₂₅ is linear or branched, saturated or unsaturated alkyl chain with 1 to 12 C atoms which may be substituted by 1 to 3 substituents selected from a hydroxy group and C1 to C6 alkoxy group, more preferably R₂₅ is a unsubstituted alkyl group with 1 to 12 C atoms, and alkyl group with 2 to 12 C atoms substituted by one or two hydroxyl groups, by one alkoxy group with 1 to 6 C atoms or by one hydroxyl and one alkoxy group with 2 to 6 C atoms, R₂₆ is linear or branched alkyl chain with 1 to 5 C atoms, and R₂₇ linear or branched, saturated or unsaturated alkyl chain with 1 to 22 C atoms, silicone compound, and natural oil.
 13. A composition for dyeing keratin fibers comprising at least one hair dye and a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid, wherein the at least one hair dye is selected from oxidative hair dye precursors and direct dyes selected from anionic, cationic and neutral dyes.
 14. The composition according to claim 13, further comprising at least one oxidizing agent.
 15. A kit for oxidative colouring keratin fibers comprising a—optionally, an aqueous composition comprising at least one organic salt or dihydroxyacetone, b—a composition comprising at least one hair dye wherein at least one hair dye is selected from oxidative hair dye precursors and direct dyes selected from anionic, cationic and neutral dyes, and c—an aqueous composition comprising at least one oxidizing agent, with the condition that at least one of the compositions a, b and c comprise a cross linked copolymer of vinylpyrrolidone, vinylimidazol, 3-methyl-1-vinylimidazolium and methacrylic acid. 